Process for producing paraffinic oils



7 Sept. 2;, 1942. V

rnocnss' FOR PRODUCING PARAFFINIC 011 s F. E. FREY EI'AL 2,296,512

Original Filed June 27, 1936 2 Sheets-Sheet 1 FREDERICK E. FRE Y PAUL. v. MCK/NNE Y WILLIAM H. wooD' Sept. 22, 1942. F HAL 2,296,512

' PROCESS FOR PRODUCING PARAFFINIC OILS Original Filed June 27. 1936 2 sheets-shet' 2 out the intermediate'conversion into Patented Sept-.22, 1942 2,296,512 PROCESS FOR PltglllllllsClNG PARAFFINIC Frederick E.- Frey,

Kinney, Pittsburgh,

Cleveland, Ohio, assignors Bartlesville, kla., Paul V. Mc-

Pa., and William H. Wood.

to Phillips Petrole v um Company, a corporation of Delaware une 27, 1936, Serial No. this application Septemher 5, 1940, Serial No. 355,529

Original application J Divided and 11 Claims.

This invention relates to the manufacture of paraflinic and saturated hydrocarbon oils, and more specifically to the prcxluction of parafiinic oils suitable for motor fuel by catalytic synthesis from hydrocarbons of lower molecular weight.

This application is a division of our copending application, Serial'No. 87,790, filed June 27, 1936, entitled Process for producing paramnic oils, now Patent 2,233,363, issued February 25, 1941.

The conversion of normally gaseous olefins into valuable hydrocarbons of higher molecular weight, suitable for motor fuels, has been effected by heat and pressure, and the use of elevated pressures eflecting'rap'id reaction and nearly complete conversion at temperatures below the pyrolysis range. The polymerization may also be peratures lower than those required for the purely thermal conversion. The hydrocarbons of higher molecular weight which result, are, in either case, composed of varying'proportions of hydrocarbons of several types, a large proportion being olefinic or unsaturated. Such olefinic polymers maybe converted into oils of saturated type by means of hydrogenation preferably of the non-destructive type.

The present invention is an improvement of the invention set forth in Freys application Serial No. 731,920, filed June 22, 1934, which issued May 21, 1935, as Patent 2,002,394, and also is an improvement of the invention set forth in Frey's application Serial No. 12,981 filed March 25, 1935, which was copending with said application of which this is a division, which is a continuationin-part of the aforesaid application and which issued January 4, 1938, as Patent No. 2,104,296.

effected with the aid of suitable catalysts at tem- It is an object of the present invention to effect 4 a process for the formation of predominantly saturated oil's at relatively low temperatures, below those required for producing such oils by thermal means, or at appreciably sultant saving in plant construction and operating expense, by effecting catalytically the polymerization reactions which involve the direct union of paraflins and olefins of lower molecular weight than the oils to be produced.

A further object of this invention is to provide a process for the production of oils of essentially saturated type without the step of hydrogenating partly olefinic polymer oils.

A still further object is to provide a process for the conversion of parafflns of low molecular weight into oils of higherv molecular weight withsimple ole-.

lower pressures, with reg5 catalytic polymerization involving union ilnic hydrocarbons prior to effecting conversion into oils.

Other objects will be apparent upon a further consideration of the following invention.

The normally gaseous olefins, ethylene, propylene, and the butylene may be converted in the process, constituting our invention, together with propane and butane which are normally gaseous, and pentanes. The conversion of pentanes, and parafiins of somewhat higher molecular weight, is desirable in circumstances inwhich their volatility is undesirably that by paraflins of low molecular weight is meant those which may yield by union with olefins, oils boiling within the gasoline range.

We have found that the union of parafiins with olefins to produce saturated hydrocarbons of higher molecular weight can be effected with known polymerization catalysts under new and appropriate conditions and in novel processes which will be presently described. Catalysts effective for the reaction are aluminum chloride chemically combined with an equimolar quantity, more or less, of lithium, sodium, calcium, or potassium chloride, and the corresponding double compounds in which chlorine is replaced by bromine. Other modifying agents added to aluminum chloride or bromide'may also be employed. Zinc chloride, zinc bromide, hydrous alumina, and hydrous alumina deposited on or combined with hydrous silica, are likewise effective for catalyzing the reaction. The catalyst is conveniently used in granular form or disposed We have found.

by extensive and practical conversion may be obtained by passing the hydrocarbon stream'into contactwith the catalyst while maintaining a reaction temperature and while adding olefin in small proportion a plurality of times in the course of the reaction, addition of olefin taking place prior to contact with the catalyst in each addition, whereby added olefin is consumed prior to each subsequent addition of additional olefin. The concentration of olefin present throughout the reaction is in this way maintained at a low value, and the paraflinic reactants at ahigh value. The temperature of the reaction is somewhat higher than the optimum for the familiar of olefin description of this I high. It will be understood- Weight per cent 0.2

Methane Butane 81.4 Butylene 1.0 Pentanes 2.8 Hexanes 1.0 Heptanes and octanes 11.8 Heptylenes and octylenes 0.5 Higher hydrocarbons 1.3

Total 100.0

As the analysis shows, the quantity of isobutane consumed was approximately equal to the isobutylene consumed. The oils formed were al- 'most wholly paraflinic in character and predominated in material distilling in the, heptaneoctane range.

Figure 2 illustrates diagrammatically a modifled apparatus for effecting the present invention, and herein hydrocarbons, consistingof olefins and parafiins, which are to be reacted, enter the process together with each other through the conduit 50 and are forced by the pump 5| through the conduit 52 to the reaction chamber 53 wherein the hydrocarbons; comprising parafilns and olefins, are brought into contact with a catalyst suitable for effecting the desired polymerization reaction.

The reacted hydrocarbons are discharged from the chamber 53 into the conduit 54 and are di- I through a reaction zone vided into two streams, one of which flows through valve 55A into conduit 55 and is forced by pump 5! through valve 5513 back into conduit 52to-be reintroduced into the reaction chamber 53. The other stream of reacted hydrocarbons flows through valve 5'iA and into conduit 51 passing into the separator 58 wherein the hydrocarbons of higher molecular weight produced by the reaction are separated from the lighter hydrocarbons and discharged through conduit 50 controlled by valve 60.

Any unreacted gases will be predominantly paraffinic and may be discharged through conduit ti, and may be reacted with additional olefin or put to any other desired use.

However, it is to be understood that it may not always be desirable, or necessary, to recycle the reacted hydrocarbons from chamber 53 back through conduits 55 and 52 for reprocessing in the reaction chamber, so therefore when desired, or conditions demand, the valves 55A and 553, which are interposed in conduit 55, may be closed.

Or it may be desirable, or necessary, to recycle the reacted hydrocarbon from chamber 53 back through the conduits 55 and 52 to the chamber again with only a minimum amount of the reacted hydrocarbons passing directly from the chamber 53 through conduits 54 and 5? to the separator be set at any desired partially closed position to limit the flow of the reacted hydrocarbons directly from chamber 53 to separator 58.

From the foregoing it should appear obvious that by control of valves 55A and 55B, and valve 51A the flow or the reacted hydrocarbons from the chamber 53 to the separator 58, or therecycling of these hydrocarbons back through the chamber 53 can be readily controlled and regulated.

We claim:

1. A continuous process for reacting parafllns of low molecular weight with normally gaseous 58, in such a case the valve A mayhydrocarbon between 100 and 400 olefins to produce predominantly paramnic oils in'the' motor fuel boiling range and of higher molecular weightwhich comprises bringing the parafilns into contact with a polymerization catalyst of the group hydrous alumina and hydrous alumina combined with or deposited on hydrous silica. in a reaction zone for a suitable reaction period while maintaining a reaction temperature C. and a pressure of at least-100 pounds per square inch, introducing normally gaseous olefins to the reaction zone a plurality of times during the reaction period while maintaining the concentration of added reacting hydrocarbons beolefin present in the low 20 per cent, withdrawing the reacted hydrocarbons from the reaction zone and separating therefrom a hydrocarbon fraction containing the predominantly parafllnic oils in the motor fuel boiling range so produced.

2. A continuous process for reacting paramns of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly parafllnic oilsmi high molecular weight in the motor fuelboiling range, which comprises passing a stream of hydrocarbons comprised of paraihns of low molecular weight in which normally gaseous olefin hydrocarbons are at a temperature between 100 and 400 C, and a pressure greater than 100 pounds per square inch, and in the presence of a polymerization catalyst of the group consisting of hydrous alumina and hydrous alumina combined with or deposited on hydrous silica, for a period of time such that reaction takes place consuming paraffin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the eflluent of said reaction zone a fraction comprising paramnic oils iuel boiling range.

for reacting paraflins in the motor 3. A continuous, process of low molecular weight olefin hydrocarbons to produce predominantly parafiinic oils of higher molecular weight in the motor fuel boiling range which comprises passing a stream of hydrocarbons comprised of paraflins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed, while at a reaction temperature between 100 and 400 C, and a pressure greater than 100 pounds per square inch, through a reaction zone in the presence of a polymerization catalyst of the group consisting of hydrous alumina and hydrous alumina combined with or deposited on hydrous silica for a period of time said olefin hydrocarbons, passing a portion of the efliuents of said reaction zone to be mixed with the hydrocarbon stream entering said zone and separating from another portion of said eiliuents predominantly paraflinic oils of. higher molecular weight in the motor fuel boiling range so pro-.

duced.

hydrocarbons in independent cyclic circulationdispersed I with normally gaseous such that reaction takes place consuming paramn hydrocarbons and afiln hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture is about 0.5 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the eflluent of said reaction zone a hydrocarbon fraction comprising paraffinic oils in the motor fuel boiling range.

11. A continuous process for reacting parafilns hydrocarbons are dispersed of unreacted unsaturated of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly paraflinic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of paraflins of low molecular weight in which nor-- mally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of hydrous alumina, for a period of time such that reaction takes place consuming paraflin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration hydrocarbons present in the mixture is about 0.5 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the eflluent of said reaction zone a hydrocarbon fraction comprising parafflnic oils in the motor fuel boiling range FREDERICK E. FREY. PAUL V. McKINNEY.

WILLIAM H. WOOD. 

